TWI830741B - Resin compositions and their applications - Google Patents

Abstract

The present invention provides a resin composition that is excellent in various properties such as heat resistance and excellent in electrical characteristics, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for manufacturing the resin composition, and a dielectric constant. and/or dielectric loss tangent reducing agent. A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by formula (1); in formula (1), X represents an organic group with 1 to 12 carbon atoms, and R ¹ ~R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a each independently represents an integer from 0 to 4.

Description

Resin compositions and their applications

The present invention relates to a resin composition. More about cured products, prepregs, metal foil-clad laminates, resin sheets, printed wiring boards, methods of manufacturing resin compositions using the aforementioned resin compositions, and reductions in dielectric constant and/or dielectric loss tangent. agent.

In recent years, semiconductors used in electronic equipment, communication equipment, personal computers, etc. have become more highly integrated and miniaturized. Along with this, various characteristics required for semiconductor package laminates (for example, metal foil-clad laminates, etc.) used in printed wiring boards have become increasingly stringent. Examples of required characteristics include low dielectric constant, low dielectric loss tangent, low thermal expansion, and heat resistance. Among them, insulator materials with large dielectric constants and dielectric loss tangents will attenuate electrical signals, thereby compromising reliability. Therefore, materials with small dielectric constants and dielectric loss tangents are required.

In order to obtain a printed wiring board with improved various characteristics, materials used as materials for the printed wiring board have been studied. For example, Patent Document 1 describes a composition that has excellent varnish storage stability and improves electrical properties, peel strength, and thermal decomposition resistance without reducing multilayer formability or heat resistance after moisture absorption. Disclosed is a bifunctional vinyl benzyl compound containing a specific polyphenylene ether skeleton, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin as constituent components, and a combination in a predetermined ratio. .

On the other hand, Patent Document 2 describes a prepreg composed of bismaleimide having a specific structure, (b) one or more liquid co-reactants optionally containing other additives, and (c) structural fiber composition. However, there is no description of electrical characteristics, etc. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2010-138364 [Patent Document 2] Japanese Patent Application Publication No. 05-25298

[Problem to be solved by the invention]

As mentioned above, resin compositions containing a cyanate ester compound and a maleimide compound that have excellent electrical properties are known. However, with recent technological innovations, further improvements in electrical characteristics are required. In addition, even if the electrical characteristics are excellent, if other properties are poor, the usefulness will be lacking. In order to solve this problem, the present invention aims to provide a resin composition containing a cyanate ester compound and a maleimide compound, which is excellent in various properties such as heat resistance and has excellent electrical characteristics; and also aims to provide a cured product, Prepreg, metal foil-clad laminate, resin sheet, printed wiring board, manufacturing method of resin composition, dielectric constant and/or dielectric loss tangent reducing agent. [Means to solve the problem]

Based on the above-mentioned subject, the inventors of the present case conducted research and found that by using a bismaleimide compound with a specific structure, it is possible to obtain a resin composition that is excellent in various properties such as heat resistance and has improved electrical characteristics. And the present invention was completed. Specifically, the aforementioned problems can be solved by the following means >1>, preferably by >2> to >18>. >1>A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1); [Chemical 1] ⁽ 1) In the formula (1) ^, integer. >2> The resin composition of >1>, wherein in formula (1), X is an alkylene group having 1 to 3 carbon atoms, and R ¹ to R ³ each independently represents a hydrogen atom, a methyl group or an ethyl group, a represents an integer from 0 to 2 each independently. >3> The resin composition of >1>, wherein the bismaleimide compound (B) is represented by the following formula (2); [Chemical 2] (2) >4> The resin composition according to any one of >1> to >3>, further containing a solvent. >5> The resin composition as in >4>, wherein the content of the aforementioned bismaleimide compound (B) accounts for 0.1 to 30 mass% in the resin composition. >6> The resin composition according to any one of >1> to >5>, wherein the content ratio of the aforementioned cyanate ester compound (A) and the aforementioned bismaleimide compound (B) is expressed by the aforementioned bismaleimide compound. The equivalent ratio of the unsaturated acyl imine group of the lysyl imine compound (B) to the cyanate ester group of the aforementioned cyanate ester compound (A) (equivalent of the unsaturated acyl imine group/equivalent of the cyanate ester group) is above 0.01 and less than 1.1. >7> The resin composition according to any one of >1> to >6>, further containing a maleimide compound, an epoxy resin, and a maleimide compound other than the bismaleimide compound (B). Phenolic resin, oxetane resin, benzene Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds More than one type in the group. >8> The resin composition according to any one of >1> to >7>, further containing a filler (C). >9> The resin composition of >8>, wherein the content of the filler (C) is 50 to 1600 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition. >10>The resin composition according to any one of >1> to >9> is a low dielectric constant material and/or a low dielectric loss tangent material. >11>A cured product is a cured product of the resin composition any one of >1> to >10>. >12> A prepreg formed from a base material and a resin composition according to any one of >1> to >10>. >13> A metal foil-clad laminate including a layer formed of at least one prepreg as in >12>, and a metal foil disposed on one or both sides of the layer formed of prepreg. >14> A resin sheet including a support and a layer formed of the resin composition according to any one of >1>> to >10> arranged on the surface of the support. >15>A printed wiring board, including an insulating layer and a conductor layer arranged on the surface of the insulating layer, the insulating layer including a layer formed of a resin composition according to any one of >1> to >10> and a conductor layer formed on the surface of the insulating layer. At least one of the layers formed by the prepreg as in >12>. >16> A method for manufacturing a resin composition, which is a method for manufacturing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1); including adding cyanide The step of mixing the acid ester compound (A), the bismaleimide compound (B) and the solvent, and the content of the aforementioned bismaleimide compound (B) accounts for 0.1 to 30 mass% in the resin composition; [Chemical 3] ⁽ 1) In the formula (1) ^, integer. >17> The manufacturing method of the resin composition as in >16>, further containing a maleimide compound selected from the group consisting of maleimide compounds other than the aforementioned bismaleimine compound (B), epoxy resin, phenolic resin, oxa Cyclobutane resin, benzene Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds More than one type in the group. >18>A dielectric and/or dielectric loss tangent reducing agent containing a bismaleimide compound (B) represented by the following formula (1); [Chemical 4] ⁽ 1) In the formula (1) ^, integer. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition containing a cyanate ester compound and a maleimide compound, which is excellent in various properties such as heat resistance and has excellent electrical characteristics. Furthermore, it is possible to provide excellent cured products, prepregs, metal foil-clad laminates, resin sheets, printed wiring boards, manufacturing methods of resin compositions, and dielectric constant and/or dielectric loss tangent reducing agents.

The contents of the present invention will be described in detail below. In addition, in this specification, "～" is used with the meaning including the numerical value written before and after it as a lower limit value and an upper limit value.

The resin composition of the present invention is characterized by containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1). [Chemistry 5] ⁽ 1) In the formula (1) ^, integer. By blending the bismaleimide compound (B) represented by the formula (1) into the cyanate ester compound (A), various properties (low water absorption, low heating loss, good varnish appearance) can be maintained and the media can be made Electricity (Dk) and dielectric loss tangent (Df) are reduced. In addition, the appearance of the prepreg and the peel strength, heat resistance, flame retardancy, etc. of the metal foil-clad laminate can be maintained at a high level. Hereinafter, the present invention will be described in detail using an embodiment of the present invention (hereinafter also referred to as “the present embodiment”) as an example.

>Cyanate ester compound (A)> The cyanate ester compound (A) in this embodiment is not particularly limited as long as it has a cyanate ester structure. Examples of the cyanate ester compound (A) include naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanate ester), naphthyl ether type cyanate ester compounds, At least one kind from the group consisting of a xylene resin type cyanate ester compound, a phenol methane type cyanate ester compound, and an adamantane skeleton type cyanate ester compound. Among these, from the viewpoint of further improving plating adhesion and low water absorption, it is preferable to select a compound selected from the group consisting of naphthol aralkyl cyanate ester compounds, naphthyl ether type cyanate ester compounds, and xylene. At least one of the group of resin-type cyanate ester compounds is preferably a naphthol aralkyl-type cyanate ester compound. These cyanate ester compounds can be prepared by known methods, and commercial products can also be used. In addition, cyanate ester compounds with naphthol aralkyl skeleton, naphthyl ether skeleton, xylene skeleton, phenol methane skeleton, or adamantane skeleton have a relatively large number of functional group equivalents, and unreacted cyanate ester There are fewer bases, so the water absorbency tends to be further reduced. In addition, mainly because it has an aromatic skeleton or an adamantane skeleton, the plating adhesion tends to be further improved.

The equivalent weight of the cyanate ester group of the cyanate ester compound (A) is preferably 200 g/eq or more, and preferably 400 g/eq or less. When a plurality of cyanate ester compounds (A) are contained, the equivalent weight of the cyanate ester group is a weighted average taking into account the mass of each cyanate ester compound contained in the resin composition.

The lower limit of the content of the cyanate ester compound (A) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and especially 20 parts by mass or more based on 100 parts by mass of the total amount of the resin components in the resin composition. Preferably, it is 30 parts by mass or more, more preferably, it is 40 parts by mass or more. When the content of the cyanate ester compound is 1 part by mass or more, more preferably 10 parts by mass or more, heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation properties are improved. tendency. The upper limit of the content of the cyanate ester compound is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less based on 100 parts by mass of the total resin components in the resin composition. 60 parts by mass or less is more preferable. The resin composition of this embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range.

>Bismaleimide compound (B) represented by formula (1)> The resin composition of this embodiment contains a bismaleimide compound (B) represented by the following formula (1). [Chemical 6] ⁽ 1) In the formula (1) ^, integer.

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an isopropyl group. The two X's can be the same or different. It should be the same. R ¹ to R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom. a should each independently represent an integer from 0 to 2, preferably 0 or 1, especially 0. The aforementioned bismaleimide compound (B) is preferably represented by formula (1-2). [Chemical 7] (1-2) In formula (1-2), X represents an organic group having 1 to 12 carbon atoms, R ¹ to R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a each independently represents An integer from 0 to 4. X, R ¹ to R ³ and a in the formula (1-2) are each synonymous with X, R ¹ to R ³ and a in the formula (1), and the ideal range is also the same. By using the bismaleimide compound represented by formula (1-2), the electrical characteristics and heat resistance (especially the suppression of heating loss) of the resin composition tend to be further improved.

The bismaleimide compound (B) represented by formula (1) is preferably represented by the following formula (2). [Chemical 8] (2)

The bismaleimide compound (B) used in this embodiment is more preferably any one of the following. [Chemical 9]

The equivalent weight of the unsaturated acyl imine group of the bismaleimide compound (B) is preferably 200 g/eq or more, and preferably 400 g/eq or less. When a plurality of bismaleimine compounds (B) are contained, the equivalent weight of the unsaturated amide group is the weighted average of the mass of each bismaleimine compound (B) contained in the resin composition.

The lower limit of the content of the bismaleimide compound (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition. More than 8 parts by mass is particularly preferred, and the amount may be 8 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more. When the content of the bismaleimide compound (B) is 1 part by mass or more, the flame resistance tends to be improved. In addition, when the bismaleimide compound (B) is contained, the upper limit of the content of the bismaleimide compound (B) is 100 parts by mass relative to the total amount of the resin components in the resin composition. It is preferably not more than 90 parts by mass, more preferably not more than 75 parts by mass, particularly preferably not more than 60 parts by mass, even more preferably not more than 45 parts by mass, even more preferably not more than 35 parts by mass, and even more preferably not more than 30 parts by mass.

In addition, the content of the bismaleimide compound (B) is preferably 0.1 to 30% by mass in the resin composition. In particular, the lower limit of the content of the bismaleimide compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and especially 20% by mass or more based on the solid content (components other than the solvent). good. The upper limit is preferably 90 mass% or less, more preferably 70 mass% or less, and particularly preferably 50 mass% or less.

Furthermore, the content of the bismaleimide compound (B) is preferably 0.1 to 30% by mass in the resin composition diluted with the solvent (in the resin composition containing the solvent). The lower limit of the content of the bismaleimide compound (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 25 mass% or less, more preferably 20 mass% or less, and particularly preferably 17.5 mass% or less. By keeping it within this range, the appearance of the varnish can be further improved, and the appearance of the prepreg and the electrical characteristics of the laminate can be further improved. The resin composition of this embodiment may contain only 1 type of bismaleimide compound (B), or may contain 2 or more types. When two or more types are contained, the total amount is preferably within the aforementioned range.

The content ratio of the cyanate ester compound (A) and the bismaleimine compound (B) in the resin composition of this embodiment is calculated based on the ratio of the unsaturated amide imine group of the bismaleimide compound (B) and The equivalent ratio of the cyanate ester groups of the cyanate ester compound (A) (equivalent of unsaturated acyl imine group/equivalent of cyanate ester group) is preferably 0.01 or more and less than 1.1. The lower limit of the above-mentioned equivalence ratio is more preferably 0.05 or more, more preferably 0.1 or more, and still more preferably 0.3 or more. Furthermore, the upper limit of the equivalent ratio is more preferably 0.9 or less, particularly preferably 0.7 or less, and still more preferably 0.5 or less. By keeping it within such a range, the effects of water absorption, electrical characteristics, and thermophysical properties can be more effectively exerted.

>Other resin components> The resin composition of this embodiment may also contain other resin components other than the cyanate ester compound (A) and the bismaleimide compound (B). Examples of other resin components include maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, and benzodiazepines. Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds It is preferable that at least one type in the group is selected from maleimide compounds other than the bismaleimine compound (B), epoxy resins, phenolic resins, oxetane resins, and benzene resins. and 㗁 It is more preferable that at least one of the group consisting of a compound and a compound having a polymerizable unsaturated group contains at least a maleimide compound other than the bismaleimide compound (B). By blending such other resin components, the aforementioned appearance can be further improved and other properties can be further improved.

>>Maleimine compounds other than bismaleimine compound (B)>> Maleimine compounds other than bismaleimine compound (B) (hereinafter also referred to as other maleimide compounds), as long as they are maleimide compounds other than bismaleimine compound (B) Imine compounds, and compounds having two or more maleimide groups in the molecule, are not particularly limited. In particular, by using a maleimide compound that has high solubility in solvents, the electrical characteristics can be improved, and the appearance of the varnish, and therefore the prepreg obtained from the varnish, can be improved. The solubility of other maleimide compounds used in this embodiment, for example, in methyl ethyl ketone at 25° C. is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The boiling point of methyl ethyl ketone is relatively low, so the drying temperature can be lowered when the solvent is dried, and the unnecessary hardening of the resin component during drying can be effectively suppressed. Examples of other maleimide compounds include maleimide compounds represented by formula (1-3). By using the maleimide compound represented by the formula (1-3), excellent heat resistance can be imparted to materials for printed wiring boards (for example, laminated boards, metal foil-clad laminated boards), etc. It can also improve peel strength, low water absorption, smear resistance, and flame resistance.

[Chemical 10] In the above formula (1-3), there are multiple R's each independently representing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n is an average value, indicating 1>n≦5. In the aforementioned formula (1-3), the plurality of R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tertiary butyl, n-pentyl, etc.), or phenyl. Among these, from the viewpoint of further improving the flame resistance and peel strength, it is preferable to use a group selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group, more preferably one of a hydrogen atom and a methyl group. Preferably, it is a hydrogen atom.

In the aforementioned formula (1-3), n is the average value, which means 1>n≦5. From the viewpoint of better solvent solubility, n is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. It may also contain two or more compounds with different n.

The maleimide compound represented by the aforementioned formula (1-3) can be prepared by a known method, and a commercially available product can also be used. An example of a commercially available product is "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

In addition to the above, other maleimide compounds include 4,4'-5,5'-diethyl-4,4'-diphenylmethane bismaleimide and 4-methyl -1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide Leimide, 4,4'-diphenylbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimide) Imide phenoxy) benzene, polyphenylmethane maleimide, and their prepolymers, prepolymers of these maleimides and amines, etc.

The equivalent weight of the unsaturated acyl imine group of other maleimine compounds is preferably 200 g/eq or more, and preferably 400 g/eq or less. When multiple other maleimine compounds are contained, the equivalent weight of the unsaturated maleimine group is the weighted average of the mass of each other maleimine compound contained in the resin composition.

When other maleimine compounds are contained, the lower limit of the content of other maleimine compounds is preferably 1 part by mass or more based on 100 parts by mass of the total amount of resin components in the resin composition, which is 10 parts by mass or more is more preferred, and 20 parts by mass or more is particularly preferred. When the content of other maleimide compounds is 1 part by mass or more, the flame resistance of the resin composition tends to be improved. Furthermore, when other maleimine compounds are contained, it is appropriate to set the upper limit of the content of other maleimine compounds to 100 parts by mass in total of the resin components in the resin composition. It is 90 parts by mass or less, more preferably 85 parts by mass or less, especially 75 parts by mass or less, more preferably 70 parts by mass or less, more preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and 45 parts by mass or less is particularly preferred. When the content of other maleimide compounds is 90 parts by mass or less, peel strength and low water absorption tend to be improved. In particular, the resin composition of this embodiment preferably contains both the bismaleimine compound represented by formula (1) and the maleimide compound represented by formula (1-3). The mass ratio of the bismaleimine compound represented by formula (1) and the maleimide compound represented by formula (1-3) in the resin composition is preferably 1:0.1~2.0, 1:1.0~ 2.0 is better, 1:1.2~1.8 is even better, and 1:1.4~1.6 is even better. With such a ratio, the appearance of the obtained varnish and the electrical properties of the cured product can be balanced at a high level. The resin composition of this embodiment may contain only one type of other maleimide compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range.

>>Epoxy resin>> The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule. Examples of the epoxy resin include bisphenol A-type epoxy resin, bisphenol E-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and phenol novolak-type epoxy resin. , bisphenol A novolak type epoxy resin, epoxy propyl ester type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, methane Phenolic novolak type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol Aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, epoxy propylamine, Glycidyl propyl ester, compounds obtained by epoxidation of double bonds such as butadiene, compounds obtained by the reaction of polysiloxy resins containing hydroxyl groups and epichlorohydrin, etc. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin are suitable. The resin is preferably biphenyl aralkyl epoxy resin.

It is preferable to contain epoxy resin within the range which does not impair the effect of the present invention. From the viewpoint of formability and adhesion, when an epoxy resin is contained, the lower limit of the content of the epoxy resin is preferably: 0.1 part by mass or more, more preferably 1 part by mass or more, especially 2 parts by mass or more. When the content of the epoxy resin is 0.1 parts by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When an epoxy resin is contained, the upper limit of the epoxy resin content is preferably 50 parts by mass or less and 30 parts by mass when the total amount of resin components in the resin composition is 100 parts by mass. It is more preferably not more than 20 parts by mass, more preferably not more than 10 parts by mass, still more preferably not more than 8 parts by mass. When the content of the epoxy resin is 50 parts by mass or less, the electrical characteristics tend to be improved. The resin composition of this embodiment may contain only one type of epoxy resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of epoxy resin. Substantially free means that the content of the epoxy resin is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Phenolic Resin>> The phenolic resin is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxyl groups in one molecule. Examples of the phenolic resin include bisphenol A-type phenolic resin, bisphenol E-type phenolic resin, bisphenol F-type phenolic resin, bisphenol S-type phenolic resin, phenol novolac resin, and bisphenol A novolac-type phenolic resin. Resin, glycidyl phenolic resin, aralkyl novolak phenolic resin, biphenyl aralkyl phenolic resin, cresol novolak type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolak resin, Multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type Phenolic resin, alicyclic phenolic resin, polyol-type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing polysiloxane resin, etc. Among them, from the viewpoint of further improving the flame resistance, it is preferable to select from the group consisting of biphenyl aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, phosphorus-containing phenolic resin, and hydroxyl-containing polysiloxane. At least one of the group consisting of resins.

It is preferable to contain phenolic resin within a range that does not impair the effect of the present invention. When a phenolic resin is contained, the content of the phenolic resin is preferably 0.1 parts by mass or more and 50 parts by mass or less when the total amount of resin components in the resin composition is 100 parts by mass. The resin composition of this embodiment may contain only one type of phenolic resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of phenolic resin. Substantially free means that the content of the phenolic resin does not reach 0.1 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Oxetane Resin>> The oxetane resin is not particularly limited as long as it is a compound having two or more oxetanyl groups. Examples of the oxetane resin include: oxetane, alkyloxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane Butane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3- Bis(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane , OXT-101 (a product of Toa Gosei Co., Ltd.), OXT-121 (a product of Toa Gosei Co., Ltd.), etc.

It is preferable to contain oxetane resin within the range which does not impair the effect of the present invention. When an oxetane resin is contained, the lower limit of the oxetane resin content is preferably 0.1 parts by mass when the total amount of resin components in the resin composition is 100 parts by mass. The above amount is more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. When the content of the oxetane resin is 0.1 parts by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When an oxetane resin is contained, the upper limit of the oxetane resin content is preferably 50 parts by mass when the total amount of resin components in the resin composition is 100 parts by mass. It is more preferably not more than 30 parts by mass, more preferably not more than 20 parts by mass, still more preferably not more than 10 parts by mass, and still more preferably not more than 8 parts by mass. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics of the resin composition tend to be further improved. The resin composition of this embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of oxetane resin. Substantially free means that the content of the oxetane resin is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Benzo Compounds >> Benzo Compounds as long as they have two or more dihydrobenzoides in one molecule Ring compounds are not particularly limited. Just benzo Examples of compounds include: bisphenol A type benzene BA-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol F type benzo BF-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol S type benzene BS-BXZ (Konishi Chemical Co., Ltd. products), etc.

It is preferable to contain benzene in a range that does not impair the effect of the present invention. compound. Contains benzo In the case of compounds, benzo The content of the compound is preferably 0.1 parts by mass or more and 50 parts by mass or less when the total amount of the resin components in the resin composition is 100 parts by mass. The resin composition of this embodiment may contain only one kind of benzene. The compound may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of benzene. The composition of compounds. Substantially does not contain benzo The content of the compound is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Compounds with polymerizable unsaturated groups>> The compound having a polymerizable unsaturated group is not particularly limited as long as it is a compound having two or more polymerizable unsaturated groups. Examples of the compound having a polymerizable unsaturated group include vinyl compounds (for example, ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, etc.), acrylic esters (for example, ( Methyl methacrylate, etc.), (meth)acrylates of monovalent or polyhydric alcohols (for example, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopenterythritol hexa(meth)acrylate, etc.), epoxy (Meth)acrylates (for example, bisphenol A-type epoxy (meth)acrylate, bisphenol F-type epoxy (meth)acrylate, etc.), benzocyclobutene resin, etc.

It is preferable to contain a compound having a polymerizable unsaturated group within a range that does not impair the effects of the present invention. When a compound having a polymerizable unsaturated group is contained, the content of the compound having a polymerizable unsaturated group is preferably 0.1 when the total amount of the resin components in the resin composition is 100 parts by mass. More than 50 parts by mass, and preferably less than 50 parts by mass. The resin composition of this embodiment may contain only one type of compound having a polymerizable unsaturated group, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Moreover, the resin composition of this embodiment may have a structure which does not substantially contain the compound which has a polymerizable unsaturated group. Substantially free means that the content of the compound having a polymerizable unsaturated group is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Modified polyphenylene ethers that have been terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide)>> Modified polyphenylene ethers that have been terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), for example, all or part of the terminals of polyphenylene ethers have carbon-carbon unsaturation. A modified product obtained by terminal modification of the substituent of the double bond. The substituent having a carbon-carbon unsaturated double bond is not particularly limited as long as it is other than a maleimide group, and examples thereof include ethylenically unsaturated groups. Examples of the ethylenically unsaturated group include: alkenyl groups such as vinyl, allyl, acrylic, methacrylic, propenyl, butenyl, hexenyl, and octenyl; cyclopentenyl and cyclohexenyl Alkenyl and other cycloalkenyl groups; vinyl benzyl and vinyl naphthyl and other alkenyl aryl groups are preferably vinyl benzyl. The term "polyphenylene ether" in this specification refers to a compound having a phenylene ether skeleton represented by the following formula (X1).

[Chemical 11] In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.

The modified polyphenylene ether may further contain repeating units represented by formula (X2) and/or repeating units represented by formula (X3); [Chemical 12] In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and are an alkyl group or phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. [Chemical 13] In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Modified polyphenylene ether can also be used in which a terminal part is functionalized with an epoxy group, an amine group, a hydroxyl group, a mercapto group, a carboxyl group, a silicon group, etc. These can be used 1 type or in combination of 2 or more types.

The method for producing modified polyphenylene ether is not particularly limited as long as the effects of the present invention can be obtained. For example, vinyl benzyl functionalization can be obtained by dissolving bifunctional phenylene ether oligomer and vinyl benzyl chloride in a solvent, adding a base under heating and stirring, and then reacting the resin. Manufactured by curing. Those obtained by carboxyl functionalization, for example, can be obtained by melting and kneading polyphenylene ether and unsaturated carboxylic acid or derivatives thereof functionalized in the presence or absence of a free radical initiator and allowing the Made by reaction. Or it can be produced by dissolving polyphenylene ether and unsaturated carboxylic acid or its functional derivative in an organic solvent in the presence or absence of a radical initiator, and reacting them in the solution.

The modified polyphenylene ether preferably contains a modified polyphenylene ether having ethylenically unsaturated groups at both ends (hereinafter, sometimes referred to as "modified polyphenylene ether (g)"). Examples of ethylenically unsaturated groups include: alkenyl groups such as vinyl, allyl, acrylic, methacrylic, propenyl, butenyl, hexenyl and octenyl; cyclopentenyl and cyclohexenyl Such as cycloalkenyl; alkenyl aryl groups such as vinyl benzyl and vinyl naphthyl, preferably vinyl benzyl. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups.

Examples of the modified polyphenylene ether (g) having an ethylenically unsaturated group at the terminal (hereinafter, may be simply referred to as modified polyphenylene ether (g)) include a structure represented by formula (G1). [Chemical 14] ( ^G1 ) In the formula ( ^G1 ) ^, represents an integer from 1 to 100, n represents an integer from 1 to 6, and q represents an integer from 1 to 4. Preferably, ^RG1 , ^RG2 , and ^RG3 are hydrogen atoms. n is preferably an integer from 1 to 4, more preferably n is 1 or 2, and even more preferably n is 1. In addition, q is preferably an integer from 1 to 3, with q being 1 or 2 being more preferred, and q being 2 being even more preferred.

The modified polyphenylene ether (g) of this embodiment is preferably represented by formula (G2). [Chemical 15] Here, -(OXO)- is preferably represented by formula (G3) and/or formula (G4); [Chemical 16] In formula (G3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are an alkyl group or phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ , and R ⁹ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. [Chemical 17] In formula (G4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In addition, -(YO)- should be represented by formula (G5); [Chemical 18] (G5) In formula (G5), R ²² and R ²³ may be the same or different, and are an alkyl group or phenyl group having 6 or less carbon atoms. R ²⁰ and R ²¹ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. At least one of a and b is not 0 and represents an integer from 0 to 100. When a and b are integers above 2, -(YO)-a or -(YO)-b may be one structural arrangement represented by formula (G5), or may be two or more structures represented by formula (G5) Arranged randomly.

Examples of -A- in formula (G4) include: methylene, ethylene, 1-methylethylene, 1,1-propylene, 1,4-phenylenebis( 1-methylethylene), 1,3-phenylenebis(1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene and other divalent organic groups, but are not limited to these.

Among the aforementioned modified polyphenylene ether (g), it is preferable that R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ and R ²¹ are alkyl groups with a carbon number of 3 or less, and R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , R ²³ are polyphenylene ethers with hydrogen atoms or alkyl groups with less than 3 carbon atoms, especially those of the formula -(OXO)- represented by (G3) or formula (G4) is formula (9), formula (10), and/or formula (11), and -(YO)- represented by formula (G5) is formula (12) ) or formula (13) is better. When a and b are integers above 2, -(YO)-a or -(YO)-b is preferably a structure in which formula (12) or formula (13) is arranged, or formula (12) and formula (13) Structures arranged randomly.

[Chemical 19] [Chemistry 20] In formula (10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and may be a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- are the same as those of -A- in formula (G4). [Chemistry 21] In formula (11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- are the same as those of -A- in formula (G4). [Chemistry 22] [Chemistry 23]

The number average molecular weight of the modified polyphenylene ether in terms of polystyrene obtained by the GPC method is preferably 500 or more and 3,000 or less. When the number average molecular weight is 500 or more, when the resin composition of this embodiment is formed into a coating film, adhesion tends to be further suppressed. When the number average molecular weight is 3000 or less, the solubility in solvents tends to be further improved. In addition, the polystyrene-converted weight average molecular weight of the modified polyphenylene ether obtained by GPC is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By being above the aforementioned lower limit value, the dielectric constant and dielectric loss tangent tend to become lower, and by being below the aforementioned upper limit value, the solubility in solvents, low viscosity, and formability are further improved. tendency. In addition, the equivalent of carbon-carbon unsaturated double bonds at the terminal end of the modified polyphenylene ether is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and more preferably 400 g to 2500 g. By being above the aforementioned lower limit value, the dielectric constant and the dielectric loss tangent tend to become lower. By being below the aforementioned upper limit, the solubility in solvents, low viscosity, and formability tend to be further improved.

The preparation method (manufacturing method) of the modified polyphenylene ether represented by formula (2) in this embodiment is not particularly limited. For example, the bifunctional phenol compound can be obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. a step of etherifying the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer with a vinyl benzyl group (vinyl benzyl etherification) steps) to manufacture. As such modified polyphenylene ether, for example, Mitsubishi Gas Chemical Co., Ltd. (OPE-2St1200, etc.) can be used.

In the oxidative coupling step, for example, a bifunctional phenol compound, a monofunctional phenol compound, and a catalyst can be dissolved in a solvent, and oxygen is blown in while heating and stirring to obtain a bifunctional phenylene ether oligomer. . The bifunctional phenol compound is not particularly limited, and examples thereof include those selected from the group consisting of 2,2', 3,3', 5,5'-hexamethyl-(1,1'-biphenol)-4,4' -Diol, 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane, and 4,4'-dihydroxy-2,2'-di At least one species from the group consisting of phenylpropane. 1. The functional phenol compound is not particularly limited, and examples include 2,6-dimethylphenol and/or 2,3,6-trimethylphenol. The catalyst is not particularly limited, and examples thereof include copper salts (for example, CuCl, CuBr, CuI, CuCl ₂ , CuBr _{2 ,} etc.), amines (for example, di-n-butylamine, n-butyldimethylamine, N,N '-Di-tert-butylethylenediamine, pyridine, N,N,N',N'-tetramethylethylenediamine, piperidine, imidazole, etc.), etc. The solvent is not particularly limited, and examples thereof include at least one selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene.

In the vinyl benzyl etherification step, for example, the bifunctional phenylene ether oligomer obtained in the oxidative coupling step and vinyl benzyl chloride can be dissolved in a solvent, and a base can be added and reacted with heating and stirring. , manufactured by curing the resin. The vinyl benzyl chloride is not particularly limited, and examples thereof include at least one selected from the group consisting of o-vinyl benzyl chloride, m-vinyl benzyl chloride, and p-vinyl benzyl chloride. The base is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinyl benzyl etherification step, in order to neutralize the base remaining after the reaction, an acid may also be used. The acid is not particularly limited. Examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. At least 1 of them. The solvent is not particularly limited, and examples thereof include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, methylene chloride, and chloroform. At least one of the groups. Examples of methods for curing the resin include a method of evaporating the solvent and drying it, a method of mixing a reaction liquid and a poor solvent, and then reprecipitating the mixture.

When modified polyphenylene ether is contained, the lower limit of the content of modified polyphenylene ether is preferably 1 part by mass or more when the total amount of resin components in the resin composition is 100 parts by mass. It is more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more. When modified polyphenylene ether is contained, the upper limit of the modified polyphenylene ether content is preferably 90 parts by mass or less when the total amount of resin components in the resin composition is 100 parts by mass. It is more preferably 85 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less. When the content of the modified polyphenylene ether is within the aforementioned range, the low dielectric loss tangent and reactivity tend to be further improved. The resin composition of this embodiment may contain only one type of modified polyphenylene ether, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range.

>>Elastomer>> The elastomer is not particularly limited, and widely known elastomers can be used. Examples of the elastomer include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene Styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluorine rubber, polysilicone rubber, their hydrogenates, their alkyl groups At least one kind from the group consisting of compounds and their copolymers. Among these, from the viewpoint of excellent electrical characteristics, it is preferable to select the group consisting of styrene butadiene, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene At least one of the group consisting of ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, their hydrides, their alkyl compounds, and their copolymers, considered to be related to modified polyethylene From the viewpoint of better compatibility of phenylene ether, at least one selected from the group consisting of styrene-butadiene rubber, butadiene rubber, and isoprene rubber is more preferred.

From the viewpoint of excellent electrical characteristics, the elastomer of this embodiment preferably has an SP value of 9 (cal/cm ³ ) ^1/2 or less. The SP value is called the dissolution parameter and is calculated from the square root of the heat of evaporation (cal/cm ³ ) ^1/2 required to evaporate 1cm ³ of liquid. Generally speaking, the smaller this value is, the lower the polarity is. The closer the value is, the higher the affinity between the two components. If the SP value of the elastomer is 9 (cal/cm ³ ) ^1/2 or less, a more suitable elastomer can be obtained. Electrical properties of resin compositions used in printed wiring boards for high-frequency applications.

If the elastomer of this embodiment has a weight average molecular weight in terms of polystyrene obtained by the GPC method of 80,000 or more and is solid at 25°C, it can be used in materials for printed wiring boards (for example, laminated boards, metal foil-clad laminates) Laminates), etc., are preferred because their crack resistance is further improved. On the other hand, if polystyrene obtained by the GPC method has a weight average molecular weight of 40,000 or less and is liquid at 25°C, the warpage of the coated film will be reduced when it is bonded to a substrate, so it is particularly suitable. As a build-up material for printed wiring boards.

It is preferable to contain the elastomer within the range which does not impair the effect of the present invention. When an elastomer is contained, the lower limit of the content of the elastomer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition. Especially for portions or more. When the content of the elastomer is 5 parts by mass or more, the electrical characteristics tend to be further improved. When an elastomer is contained, the upper limit of the content of the elastomer is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 70 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition. Particularly preferably not more than 60 parts by mass, still more preferably not more than 60 parts by mass, still more preferably not more than 50 parts by mass. When the content of the elastomer is 20 parts by mass or less, combustion resistance tends to be improved. The resin composition of this embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of elastomer. Substantial absence means that the content of the elastomer is less than 1 part by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>>Active ester compound>> The active ester compound is not particularly limited, and examples thereof include compounds having two or more active ester groups per molecule. The active ester compound may be a linear or branched or cyclic compound. Among these, from the viewpoint of further improving heat resistance, an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferred. An active ester compound obtained by reacting an acid compound and one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferred. In order to make a carboxylic acid compound and a carboxylic acid compound have a phenolic hydroxyl group An aromatic compound obtained by reacting an aromatic compound and having two or more active ester groups in one molecule is particularly preferred. It is a compound having two or more carboxylic acids in one molecule and a compound having a phenolic hydroxyl group. Aromatic compounds obtained by reacting aromatic compounds and having two or more active ester groups in one molecule are particularly preferred. The carboxylic acid compound may be selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of further improving heat resistance, it is preferable to select one or more from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid. It is more preferable that at least one type of formic acid is selected from the group consisting of isophthalic acid and terephthalic acid. The thiocarboxylic acid compound may be one or more selected from the group consisting of thioacetic acid and thiobenzoic acid. The aforementioned phenol compound or naphthol compound may be selected from the group consisting of hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, and methylated bisphenol. F. Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phlorigocinol, phloroglucinol, dicyclopentadienyldiphenol , and phenol novolac. From the viewpoint of further improving heat resistance and solvent solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methyl bisphenol A, and methyl bisphenol A are preferred. Bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene , dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phloroglucinol, dicyclopentadienyldiphenol, phenol novolac, selected from o Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, root Preferably, at least one of the group consisting of pyrogallol, phloroglucinol, dicyclopentadienyl diphenol, and phenol novolak is selected from the group consisting of 1,5-dihydroxynaphthalene, 1,6- The group consisting of dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolac Particularly preferably, at least one of them is selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak. One or more species from the group (preferably one or more species selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol) is particularly preferred . The aforementioned thiol compound may be selected from the group consisting of benzene dithiol and trithiol. One or more species from the group consisting of dithiols. Furthermore, from the viewpoint of further improving the compatibility with the epoxy resin, the active ester compound is preferably a compound having two or more carboxylic acids in one molecule and containing an aliphatic chain, in order to further improve the heat resistance. From this point of view, it is preferable to be a compound with an aromatic ring. More specific examples of the active ester compound include those described in Japanese Patent Application Laid-Open No. 2004-277460.

The active ester compound can be a commercially available product or can be prepared by a known method. Examples of commercially available products include compounds containing a dicyclopentadienyl diphenol structure (for example, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all products of DIC Co., Ltd.), etc.), phenol novolaks acetyl compounds (for example, DC808 (manufactured by Mitsubishi Chemical Co., Ltd.)), and benzyl compounds of phenol novolac (for example, YLH1026, YLH1030, YLH1048 (all products of Mitsubishi Chemical Co., Ltd.)). From the viewpoint of further improving the storage stability of the varnish and the low thermal expansion rate of the hardened product, EXB9460S is preferred.

As for the preparation method of the active ester compound, it can be prepared by a known method, for example, it can be obtained by the condensation reaction of a carboxylic acid compound and a hydroxy compound. Specific examples include using (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound in an amount of 1 mol relative to the carboxyl group or chloride halide group of (a). , a method in which the reaction is carried out in a ratio of (b) phenolic hydroxyl group of 0.05 to 0.75 mole and (c) 0.25 to 0.95 mole.

It is preferable to contain an active ester compound within a range that does not impair the effects of the present invention. When an active ester compound is contained, the content of the active ester compound is preferably 1 part by mass or more and 90 parts by mass or less based on 100 parts by mass of the total amount of resin components in the resin composition. The resin composition of this embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. Furthermore, the resin composition of this embodiment may be substantially free of active ester compounds. Substantially free means that the content of the active ester compound is less than 1 part by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

When the resin composition of this embodiment does not contain or substantially does not contain the filler (C) described below, the total amount of the resin components is preferably 70 mass % or more of the components other than the solvent in the resin composition, and is 80 mass %. % or more is more preferred, and 90 mass% or more is particularly preferred. When the resin composition of this embodiment contains the filler (C) described below, the total amount of the resin components is preferably 30% by mass or more of the components other than the solvent in the resin composition, more preferably 35% by mass or more, and 40% by mass. The above is better. The upper limit is preferably 70 mass% or less, more preferably 65 mass% or less, and even more preferably 60 mass% or less. In either case, it is preferable that at least 90% by mass of the resin component consists of the cyanate ester compound (A), the bismaleimide compound (B) represented by the formula (1), and other maleimide compounds.

>Filling material(C)> In order to improve low dielectric properties, low dielectric loss tangent, flame resistance, and low thermal expansion, the resin composition of this embodiment preferably contains a filler (C). As the filler (C) used in this embodiment, a known filler can be appropriately used, and its type is not particularly limited, and those commonly used in this field can be preferably used. Specific examples include natural silica, fused silica, synthetic silica, amorphous silica, silica aerosol (AEROSIL), hollow silica and other silicas, and white carbon black. , titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated products (heating aluminum hydroxide Processed to reduce part of the crystal water), boehmite, metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide or zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, Calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including E Glass fine powders such as glass, T glass, D glass, S glass, Q glass, etc.), inorganic fillers such as insulating glass, spherical glass, and other rubbers such as styrene type, butadiene type, and acrylic type Powder, core-shell rubber powder, polysilicone resin powder, polysilicone rubber powder, polysilicone composite powder and other organic fillers, etc. Among these, one or two or more types selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferred, and silica is more preferred. The silica is preferably spherical silica. Spherical silica can also be hollow silica. By using these fillers (C), the thermal expansion characteristics, dimensional stability, flame retardancy and other characteristics of the resin composition are improved.

The content of the filler (C) in the resin composition of this embodiment can be appropriately set according to the desired characteristics and is not particularly limited. When the total amount of the resin components in the resin composition is 100 parts by mass, it is preferably 10 It is more than 20 parts by mass, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and more preferably 75 parts by mass or more. The upper limit value is preferably 1,600 parts by mass or less, more preferably 1,200 parts by mass or less, especially 1,000 parts by mass or less, more preferably 750 parts by mass or less, still more preferably 500 parts by mass or less, and 300 parts by mass or less. More preferably, it is 250 parts by mass or less, even more preferably 200 parts by mass or less. The resin composition of this embodiment may contain only one type of filler (C), or may contain two or more types. When two or more types are contained, the total amount is preferably within the aforementioned range. On the other hand, in this embodiment, the resin composition may be substantially free of the filler (C). Substantially free means that the content of the filler (C) does not reach 1% by mass of the content of the resin component, and is preferably 0.1% by mass or less.

Here, when using the filler (C), it is preferable to use a silane coupling agent and/or a moist dispersing agent. Silane coupling agents generally used for surface treatment of inorganic substances can be preferably used, and their types are not particularly limited. Specific examples include: aminosilanes such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; γ-epoxy Epoxysilane series such as propoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-methacryloxypropyltrimethoxysilane, ethylene Tris(β-methoxyethoxy)silane and other vinyl silane series; N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride Cationic silane series; phenyl silane series, etc. Silane coupling agents can be used alone, or two or more types can be used in combination. In addition, the wetting dispersing agent can be suitably used for those commonly used in paints, and its type is not particularly limited. It is preferable to use a copolymer-based wetting and dispersing agent. Specific examples include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010, BYK-W903, BYK- manufactured by BYK Japan Co., Ltd. W940 etc. The moistening and dispersing agent can be used alone, or two or more types can be used in combination.

The content of the silane coupling agent is not particularly limited, but may be about 1 to 5 parts by mass relative to 100 parts by mass of the total resin components in the resin composition. The content of the dispersant (especially the wet dispersant) is not particularly limited, but may be, for example, about 0.5 to 5 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

>Curing accelerator> The resin composition of this embodiment may further contain a curing accelerator. The hardening accelerator is not particularly limited, and examples thereof include: imidazoles such as triphenylimidazole; benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and diperoxyphthalate. Organic peroxides such as di-tert-butyl formate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-Ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as phosphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol Category: lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetyl acetonate and other organic metals Salts; those obtained by dissolving these organic metal salts in compounds containing hydroxyl groups such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; dioctyltin oxide, other alkyltin, Organotin compounds such as alkyl tin oxide, etc. The hardening accelerator is preferably imidazoles and organic metal salts, and a combination of imidazoles and organic metal salts is more preferred.

When a hardening accelerator is contained, the lower limit of the content of the hardening accelerator is preferably 0.005 parts by mass or more and 0.01 parts by mass or more based on 100 parts by mass of the total resin component in the resin composition. More preferably, it is 0.1 part by mass or more. In addition, the upper limit of the content of the aforementioned hardening accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less based on 100 parts by mass of the total amount of resin components in the resin composition. . A hardening accelerator can be used individually by 1 type, or in combination of 2 or more types. When two or more types are used, the total amount should be within the aforementioned range.

>Solvent> The resin composition of this embodiment may also contain a solvent, and preferably contains an organic solvent. At this time, the resin composition of this embodiment is at least a part of the above-mentioned various resin components, preferably a state in which all of the resin components are dissolved in the solvent or miscible with the solvent (solution or varnish). The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve at least part, preferably all, of the various resin components mentioned above or can be miscible with each other. Examples of polar organic solvents include: ketones ( For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellulose (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (such as ethyl lactate, methyl acetate, Ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (for example, dimethoxyacetamide, dimethylformamide etc.), and examples of non-polar organic solvents include aromatic hydrocarbons (for example, toluene, xylene, etc.). When the resin composition of this embodiment contains a solvent, its content is not particularly limited. For example, it may be 1% by mass or more, 10% by mass or more, 30% by mass or more, or 40% by mass of the resin composition. above. Moreover, the upper limit may be 99 mass% or less, 80 mass% or less, 70 mass% or less, or 60 mass% or less. A solvent can be used individually by 1 type, or in combination of 2 or more types. When two or more types are used, the total amount should be within the aforementioned range. In the resin composition of this embodiment, the solid content in the resin composition is preferably 10 mass% or more, more preferably 15 mass% or more, particularly 20 mass% or more, and still more preferably 30 mass% or more. , it can also be 40 mass% or more or 50 mass% or more. In addition, the upper limit of the solid content is preferably 90 mass% or less, more preferably 80 mass% or less, especially 70 mass% or less, and may also be 60 mass% or less. In addition, the solid content refers to components other than the solvent in the resin composition.

>Other ingredients> In addition to the above-mentioned components, the resin composition of this embodiment may also contain thermoplastic resins, various polymer compounds such as oligomers thereof, and various additives within a range that does not impair the effects of the present invention. Additives can be listed: flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, flow regulators, lubricants, defoaming agents, Dispersants, leveling agents, gloss agents, polymerization inhibitors, etc. These additives can be used individually by 1 type, or in combination of 2 or more types. Furthermore, the resin composition of this embodiment may be substantially free of flame retardants. Substantially free means that the content of the flame retardant does not reach 0.01 parts by mass relative to 100 parts by mass of the total amount of the resin composition, and is preferably 0 parts by mass. Even if the resin composition of this embodiment contains substantially no flame retardant, it is valuable in that it can maintain high flame retardancy. Specifically, the flame retardancy of the resin composition of this embodiment when molded into a material (printed wiring board, etc.) with a thickness of 0.8 mm (further 0.4 mm) according to UL (Underwriters Laboratories Inc.) standards can be V -0. The flame retardancy was measured according to the description of the Examples mentioned later.

>Detailed form of resin composition> Hereinafter, a more specific aspect of this embodiment will be described. Of course, this embodiment is not limited to these. A first specific example of the resin composition of this embodiment is a form in which the solid content of the resin composition contains 90 mass % or more (preferably 95 mass % or more) of the resin component. In this embodiment, the resin component preferably contains a cyanate ester compound (A), a bismaleimide compound (B) represented by formula (1), and other maleimide compounds. The resin composition of the first specific example may be formed into a 0.8 mm thick test piece and have a dielectric constant (Dk) of 10 GHz or less of 3.0 or less or 2.8 or less. The lower limit value of the aforementioned dielectric constant is ideally 0, but in reality it is 2.0 or more. Furthermore, the dielectric loss tangent (Df) of the resin composition of the first specific example molded into a 0.8 mm thick test piece at 10 GHz may be 0.0050 or less, may be less than 0.0045, or may be 0.0044 or less. The lower limit value of the aforementioned dielectric constant is ideally 0, but in reality it is 0.0020 or more. The dielectric constant and the dielectric loss tangent were measured using the method described in the Examples described later. In the resin composition of the first specific example, the 1% mass reduction temperature when molded into a 0.8 mm thick test piece may be 370°C or higher, or may be 380°C or higher. The upper limit of the aforementioned 1% mass reduction temperature is not particularly specified, but is actually below 420°C. The mass reduction rate of the resin composition of the first specific example formed into a 0.8 mm thick test piece at 450°C may be 19.0% or less, or 18.0% or less. The lower limit of the aforementioned mass reduction rate at 450°C is ideally 0, but in reality it is more than 10%.

The second specific example of the resin composition of this embodiment is that the solid content of the resin composition contains 5 to 70 mass % (preferably 20 to 60 mass %) of the resin component, and 95 to 30 mass % (preferably 80 mass %). ~40% by mass) of filler material. In this embodiment, the resin component preferably contains a cyanate ester compound (A), a bismaleimide compound (B) represented by formula (1), and other maleimide compounds. The filling material should be spherical silica.

>Method for producing a resin composition> The method for producing a resin composition according to this embodiment is a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the formula (1). The manufacturing method includes the step of mixing a cyanate ester compound (A), a bismaleimide compound (B) and a solvent, the content of the bismaleimide compound (B) accounting for 0.1 to 30 mass% (preferably 0.1 to 20 mass%). In this way, by setting the content of the bismaleimide compound (B) within the aforementioned range, it can be appropriately dissolved in the solvent, and the appearance of the varnish can be further improved, thereby further improving the appearance of the prepreg. . In particular, by using the bismaleimide compound represented by the above formula (1-2) as the bismaleimide compound represented by the formula (1), the aforementioned appearance can be further improved. In addition, the manufacturing method of the resin composition of this embodiment preferably further contains a maleimide compound selected from the group consisting of a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenolic resin, and an oxetane. Alkane resin, benzene Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds One or more of the group consisting of a maleimide compound selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resin, phenolic resin, oxetane resin, benzene and 㗁 More preferably, one or more types from the group consisting of a compound and a compound having a polymerizable unsaturated group. By blending such other resin components, the aforementioned appearance can be improved and other properties can be better.

>Use> The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of this embodiment can be ideally used as a low dielectric constant material and/or a low dielectric loss tangent material as an insulating layer of a printed wiring board or a semiconductor package material. The resin composition of this embodiment can be ideally used as a material constituting prepregs, metal foil-clad laminates using prepregs, resin sheets, and printed wiring boards. The resin composition of this embodiment is used as a material for layered (including film-like, sheet-like, etc.) molded products such as insulating layers of printed wiring boards, prepregs, and resin sheets. , its thickness should be more than 5 μm, preferably more than 10 μm. The upper limit of the thickness of the molded product is preferably 200 μm or less, more preferably 180 μm or less. In addition, when the thickness of the said layered molded article is obtained by impregnating a base material, such as glass cloth, with the resin composition of this embodiment, it means including the thickness of a base material. The material made of the resin composition of this embodiment can be used for pattern formation by exposure and development, or can be used without exposure and development. Especially suitable for applications where exposure and development are not required.

>>Prepreg>> The prepreg system of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment. The prepreg of this embodiment can be prepared by applying (for example, impregnating or coating) the resin composition of this embodiment to a base material, and then heating (for example, drying at 120 to 220° C. for 2 to 15 minutes). etc.) to semi-harden it. At this time, the adhesion amount of the resin composition (including the cured product of the resin composition) relative to the base material, that is, the total amount of the resin composition (including filler) relative to the semi-cured prepreg is preferably 20 to 99 mass% range.

The base material is not particularly limited as long as it is used for various printed wiring board materials. Examples of the material of the base material include glass fiber (for example, E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.) and inorganic fibers other than glass. (for example, quartz, etc.), organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, etc.). The form of the base material is not particularly limited, and examples thereof include base materials composed of layered fibers such as woven fabrics, nonwoven fabrics, rovings, strand mats, and surface mats. In particular, a substrate made of long fibers such as glass cloth is suitable. Here, long fibers refer to those whose number average fiber length is 6 mm or more, for example. These base materials can be used individually by 1 type, or in combination of 2 or more types. Among these base materials, from the perspective of dimensional stability, it is appropriate to use fabrics that have been subjected to ultra-fiber opening treatment and hole plugging treatment. From the perspective of moisture absorption and heat resistance, it is appropriate to use epoxy silane treatment, amine-based fabrics, etc. Glass fabrics that have been surface-treated with silane coupling agents such as silane treatment are suitable for L-glass, NE-glass, Q-glass, etc., which exhibit low dielectric properties and low dielectric loss tangent from the viewpoint of electrical properties. Low dielectric glass cloth composed of glass fiber. The thickness of the base material is not particularly limited, but may be about 0.01 to 0.19 mm, for example.

>>Metal foil-clad laminate>> The metal foil-clad laminate of this embodiment includes a layer made of at least one piece of the prepreg of this embodiment, and a single layer disposed on the layer made of the prepreg. Metal foil on one or both sides. The metal foil-clad laminated board of this embodiment can be formed by arranging at least one piece (preferably two or more stacked pieces) of the prepreg of this embodiment, arranging metal foil on one or both sides thereof, and laminating it. method of production. More specifically, it can be produced by arranging metal foils such as copper and aluminum on one or both sides of the prepreg and performing lamination molding. The number of prepreg sheets is preferably 1 to 10, more preferably 2 to 10, even more preferably 2 to 7. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (copper foil) is not particularly limited, but may be 1.5 μm or more, and may be about 2 to 70 μm. Examples of the molding method include methods commonly used when molding laminated boards and multilayer boards for printed wiring boards. More specifically, examples include the use of multi-stage presses, multi-stage vacuum presses, continuous forming machines, and autoclaves. A molding machine, etc., performs laminate molding under the conditions of a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100kg/ ^cm2 . Moreover, a multilayer board can also be produced by combining the prepreg of this embodiment with a separately produced inner layer wiring board (also called an inner layer circuit board) and laminating them. As for the manufacturing method of the multilayer board, for example, a metal foil (copper foil) of about 35 μm can be placed on both sides of a prepreg of this embodiment, and the inner layer circuit can be formed after lamination molding by the above-mentioned molding method. The circuit is blackened to form an inner circuit board. After that, the inner circuit board and the prepreg of this embodiment are alternately arranged one by one, and a metal foil (copper foil) is further arranged on the outermost layer. , according to the aforementioned conditions, it is better to perform lamination molding under vacuum to produce multi-layer boards. The metal foil-clad laminated board of this embodiment can be ideally used as a printed wiring board.

>>Printed wiring board>> The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer. The insulating layer includes a layer made of the resin composition of this embodiment and a prepreg layer of this embodiment. At least one of the layers of body formation. Such a printed wiring board can be manufactured according to conventional methods, and its manufacturing method is not particularly limited. Below, an example of a manufacturing method of a printed wiring board is shown. First, a metal foil-clad laminate such as the above-mentioned copper foil laminate is prepared. Then, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, and an inner layer substrate is produced. If necessary, surface treatment is performed on the inner circuit surface of the inner substrate to improve the bonding strength, and then a required number of the above-mentioned prepregs are stacked on the inner circuit surface, and the outer circuit is further laminated on the outside. The metal foil is heated, pressed and formed into one piece. In this manner, a multilayer laminate is produced in which an insulating layer composed of a base material and a cured product of a thermosetting resin composition is formed between the inner circuit and the metal foil for the outer circuit. Then, after the multi-layer laminate board is drilled for through holes and via holes, metal for connecting the inner circuit and the outer circuit is formed on the wall of the hole. The metal foil conductive plating film is further etched to form an outer circuit by etching the metal foil for the outer circuit, thereby producing a printed wiring board.

The printed wiring board obtained in the above production example has a structure including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. That is, the prepreg of the present embodiment described above (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated or coated on the base material), the metal foil-clad laminate of the present embodiment described above The layer formed of the resin composition in the board serves as the insulating layer of this embodiment.

>>Resin sheet>> The resin sheet of this embodiment includes a support and a layer formed of the resin composition of this embodiment arranged on the surface of the support. Resin sheets can be used as stacking films or dry film solder resists. The manufacturing method of the resin sheet is not particularly limited. For example, a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied (coated) to a support and dried to obtain a resin sheet.

Examples of the support used here include: polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and films based on these films. Release films coated with a release agent on the surface, organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, plate-shaped ones such as glass plates, SUS plates, and FRP, are not particularly limited.

Examples of the coating method (coating method) include coating a support with a solution obtained by dissolving the resin composition of the present embodiment in a solvent using a coating bar, a die coater, a blade coater, a Baker coater, etc. method on. In addition, after drying, the support may be peeled off or etched from the resin sheet obtained by laminating the support and the resin composition to form a single-layer sheet. In addition, a single-layer sheet can be obtained without using a support by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-shaped mold cavity and drying the solution to form a sheet. .

In addition, in the production of the single-layer sheet or the resin sheet of this embodiment, the drying conditions when removing the solvent are not particularly limited. It is considered that if the temperature is low, the solvent will easily remain in the resin composition, and if the temperature is high, the curing of the resin composition will proceed. In terms of performance, it is advisable to conduct it at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, in the single-layer sheet or the resin sheet, the resin composition can be used in an uncured state after only drying the solvent, or in a semi-cured (B-staged) state if necessary. In addition, the thickness of the single layer or the resin layer of the resin sheet in this embodiment can be adjusted by the solution concentration and coating thickness of the resin composition of this embodiment, and is not particularly limited. Generally, when the coating thickness becomes thicker, the solvent becomes easier to dry. In terms of residue, it is suitable to be 0.1 to 500 μm.

>Reducing agent for dielectric constant and/or dielectric loss tangent> The dielectric constant and/or dielectric loss tangent reducing agent of this embodiment contains the bismaleimide compound (B) represented by formula (1). By blending the bismaleimide compound represented by the formula (1) with a maleimide compound other than the cyanate ester compound (A) and the bismaleimide compound (B), and other resin components, It can reduce the dielectric constant and/or the dielectric loss tangent of the resin composition. In particular, the dielectric constant and/or dielectric loss tangent reducing agent of this embodiment is effective as a dielectric loss tangent reducing agent. The ideal range of the bismaleimide compound represented by formula (1) is the same as above. [Example]

The present invention will be described in more detail below with reference to examples. The materials, usage amounts, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

>Synthesis Example 1 Synthesis of naphthol aralkyl cyanate ester compound (SNCN)> 300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) (converted to 1.28 mol of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol relative to 1 mol of hydroxyl group) were dissolved in 1800 g of methylene chloride, and this was used as solution 1. Combine 125.9g (2.05mol) cyanogen chloride (1.6mol per mole of hydroxyl group), 293.8g methylene chloride, 194.5g (1.92mol) 36% hydrochloric acid (1.5 mole per mole of hydroxyl group), and 1205.9 water g. Keep the liquid temperature at -2~-0.5°C with stirring, and inject solution 1 over 30 minutes. After the injection of solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl group) dissolved in 65 g of dichloromethane was injected over 10 minutes. After the injection of solution 2 is completed, stir at the same temperature for 30 minutes to complete the reaction. After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The conductivity of the wastewater in the fifth wash was 5 μS/cm, and it was confirmed that the ionic compounds to be removed could be fully removed by washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the intended naphthol aralkyl cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight of the obtained SNCN was 600. In addition, the IR spectrum of SNCN shows absorption at 2250 cm ^-1 (cyanate group) and does not show absorption of hydroxyl groups. The equivalent weight of the cyanate ester group of the obtained SNCN was 256g/eq.

>Synthesis Example 2 Synthesis of bismaleimide compound (BMI-Bisanilin-M)> In a flask equipped with a stirrer, nitrogen inlet pipe, Dean-Stark device, cooler and thermometer, add 17.23g (50.0mmol) 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene manufactured by Tokyo Chemical Industry Co., Ltd., and 120.0 g of N,N-dimethylformamide as a solvent. Add nitrogen while stirring to dissolve. 10.8 g (110 mmol) of maleic anhydride was added to the solution, and the mixture was stirred at room temperature overnight. Thereafter, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were added, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurs, and part of them is condensed in the cooler. After the water and toluene captured in the Dean-Stark device are separated, only the toluene is returned to the system, and a part of the toluene is distilled from the upper part of the cooling pipe to the outside of the system by the flow of nitrogen. After cooling the reaction mixture, toluene was distilled off using an evaporator. Thereafter, the obtained solution was added to 1% by mass baking soda water to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N,N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was filtered and dried. This operation was repeated three times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%). The equivalent weight of the maleimide group of the obtained BMI-Bisanilin-M was 252.3 g/eq. [Chemistry 24]

>Synthesis Example 3 Synthesis of bismaleimide compound (BMI-Bisanilin-P)> In a flask equipped with a stirrer, nitrogen inlet pipe, Dean-Stark device, cooler and thermometer, add 17.23g (50.0mmol) 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene manufactured by Tokyo Chemical Industry Co., Ltd. and 120.0 g of N,N-dimethylformamide as a solvent, side by side Add nitrogen while stirring to dissolve. 10.8 g (110 mmol) of maleic anhydride was added to the solution, and the mixture was stirred at room temperature overnight. Thereafter, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were added, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurs, and part of them is condensed in the cooler. After the water and toluene captured in the Dean-Stark device are separated, only the toluene is returned to the system, and a part of the toluene is distilled from the upper part of the cooling pipe to the outside of the system by the flow of nitrogen. After cooling the reaction mixture, toluene was distilled off using an evaporator. Thereafter, the obtained solution was added to 1% by mass baking soda water to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N,N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was filtered and dried. This operation was repeated three times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%). The functional group equivalent weight of the obtained BMI-Bisanilin-P was 252.3g/eq. [Chemical 25]

>Example 1> Using methyl ethyl ketone as a solvent, 50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, and 30 parts by mass of biphenyl aralkyl type polymaleimide were mixed. Compound ("MIR-3000", manufactured by Nippon Kayaku Co., Ltd., the equivalent of maleimide group is 275g/eq), 0.5 parts by mass of TPIZ (2,4,5-triphenylimidazole, hardening accelerator), 0.10 parts by mass of zinc octoate ("Oct-Zn", hardening accelerator manufactured by Nippon Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone and mixed so that the solid content concentration became 50 mass %, and a varnish was obtained. In addition, the content of each component mentioned above represents the solid content amount. The appearance of the obtained varnish was evaluated according to the method described below.

Methyl ethyl ketone was evaporated and distilled off from the obtained varnish, thereby obtaining a mixed resin powder. The mixed resin powder was filled into a mold with a side of 100 mm and a thickness of 0.8 mm, and vacuum pressing was performed for 120 minutes under the conditions of a pressure of 40 kg/cm ² and a temperature of 230°C to obtain a test piece of a hardened product with a side of 100 mm and a thickness of 0.8 mm. For the obtained 0.8mm thick test piece, the water absorption, electrical properties (Dk and Df), and heating loss were measured according to the following methods.

>>Varnish appearance>> The appearance of the obtained varnish was visually evaluated as follows. Ratings A to C are practical levels. A: Uniform and no precipitates were observed. B: Uniform and almost no precipitates are observed. C: Slight unevenness and some precipitates were observed. D: It is uneven and many precipitates are observed.

>>Water Absorption Rate>> Using the obtained 0.8mm thick test piece, a pressure cooker (PCT) testing machine was used in accordance with JIS C6481, and the water absorption rate was calculated from the weight change after steam treatment at 120°C, 0.1MPa, and 5 hours. However, in JIS C6481, the sample size is changed from 0.8mm thick test piece to 30mm×30mm. The pressure cooker testing machine is model PC-3 manufactured by Hirayama Seisakusho Co., Ltd. The results are shown in Table 1 below.

>>Electrical Characteristics (Dk and Df)>> For the obtained 0.8mm thick test piece, a perturbation method cavity resonator was used to measure the dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz. The perturbation method cavity resonator uses Agilent8722ES, a product of Agilent Co., Ltd. The results are shown in Table 1 below.

>>Heating reduction>> Thermogravimetric analysis of the hardened material was performed using a thermogravimetric measuring device under a nitrogen atmosphere at a temperature rising rate of 10°C/min. The thermogravimetric measuring device was "TGA5200" manufactured by SII NanoTechnology Co., Ltd. The results are shown in Table 1 below.

>Example 2> The BMI-Bisanilin-M in Example 1 was changed to an equal amount of BMI-Bisanilin-P obtained in Synthesis Example 3, and the other procedures were carried out in the same manner. The results are shown in Table 1 below.

>Comparative Example 1> BMI-Bisanilin-M in Example 1 was not used, and the content of MIR-3000 was changed to 50 parts by mass. The other procedures were carried out in the same manner. The results are shown in Table 1 below.

>Comparative example 2> SNCN and MIR-3000 in Example 1 were not used, and the content of BMI-Bisanilin-M was changed to 100 parts by mass. The other procedures were carried out in the same manner. The results are shown in Table 1 below.

>Comparative Example 3> SNCN, MIR-3000 and BMI-Bisanilin-M in Example 1 were not used, and the content of BMI-Bisanilin-P was changed to 100 parts by mass. The other procedures were carried out in the same manner. The results are shown in Table 1 below.

[Table 1]

From the foregoing results, it can be seen that the resin compositions of Examples 1 and 2 can maintain the same good varnish appearance and low water absorption as Comparative Example 1, and have smaller heating losses than Comparative Example 1, and have improved electrical characteristics. In particular, Df is significantly reduced. In Comparative Examples 2 and 3, the varnish appearance evaluation was D, indicating that the varnish could not be used practically.

>Example 3> Using methyl ethyl ketone as a solvent, 50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, and 30 parts by mass of biphenyl aralkyl type polymaleimide were mixed. Compound ("MIR-3000", manufactured by Nippon Kayaku Co., Ltd.), 100 parts by mass of spherical silica (SC2050-MB, manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm), 0.5 parts by mass of TPIZ (2, 4,5-triphenylimidazole, hardening accelerator) and 0.10 parts by mass of zinc octoate ("Oct-Zn", manufactured by Nippon Chemical Industry Co., Ltd., hardening accelerator) were dissolved in methyl ethyl ketone and mixed so that the solid content concentration became 50 mass %, get varnish. In addition, each content mentioned above represents the solid content amount. The appearance of the obtained varnish was evaluated according to the method described below.

The obtained varnish was impregnated and coated on E glass cloth with a thickness of 0.1 mm, and heated and dried at 165° C. for 5 minutes using a dryer (pressure-resistant and explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.) to obtain 50 mass of a resin composition. %, glass cloth 50% by mass of prepreg. The appearance of the obtained prepreg was evaluated according to the method described below. In a state where 4 or 8 pieces of the obtained prepregs are stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) is placed on both sides, and the pressure is 40 kg/cm ² and the temperature is 220°C. The conditions were followed by vacuum pressing for 120 minutes to obtain copper-clad laminated boards with thicknesses of 0.4mm and 0.8mm. For the obtained copper foil laminated board, the peel strength, bending physical properties, water absorption, electrical properties (Dk and Df), glass transition temperature, flame retardancy, thermal expansion rate, heating loss and thermal conductivity were measured.

>>Varnish appearance>> The appearance of the obtained varnish was visually evaluated as follows. Ratings A to C are practical levels. A: Uniform and no precipitates were observed. B: Uniform and almost no precipitates are observed. C: Slight unevenness and some precipitates were observed. D: It is uneven and many precipitates are observed.

>>Prepreg Appearance>> The appearance of the obtained prepreg was visually evaluated as follows. Ratings A to C are practical levels. A: Uniform and no precipitates were observed. B: Uniform and almost no precipitates are observed. C: Slight unevenness and some precipitates were observed. D: It is uneven and many precipitates are observed.

>>Peel strength>> A test piece (30 mm × 150 mm × thickness 0.8 mm) obtained by cutting the 0.8 mm thick copper clad laminate obtained above was used to test the copper clad laminate for printed wiring boards in accordance with JIS C6481 (refer to 5.7 Peel strength.), measure the peel strength of the copper foil three times, and define the average of the lower limit values as the measured value. The results are shown in Table 2.

>>Bending properties>> The copper foil located on the surface of the 0.8mm thick copper-clad laminate obtained above was removed by etching, and an Autograph testing machine was used in accordance with JIS K6911 to measure the two end portions of the test piece supported by fulcrums to form two-end support beams, and The bending strength is obtained from the maximum bending stress when a concentrated load is applied to the central part of the upper part. In addition, a test piece with the copper foil of the copper-clad laminate board removed was used, and an Autograph testing machine was used in accordance with JIS K6911 to measure the straight line of the test piece relative to the load deflection curve within the elastic limit in the form of bending stress per unit strain. The bending modulus is obtained by measuring the deformation resistance of the bending stress of the part. The Autograph testing machine uses AG-Xplus manufactured by Shimadzu Corporation. The results are shown in Table 2.

>>Water Absorption Rate>> The obtained 0.8mm thick copper-clad laminated board was cut into 30mm×30mm samples, and a pressure cooker (PCT) testing machine was used in accordance with JIS C6481, and the sample was processed at 120°C, 0.1MPa, and 5 hours. Calculate the water absorption rate from the change in weight. The pressure cooker testing machine is model PC-3 manufactured by Hirayama Seisakusho Co., Ltd. The results are shown in Table 2.

>>Electrical Characteristics>> The dielectric constant (Dk) and dielectric loss tangent (Dk) at 2 GHz and 10 GHz were measured using samples obtained by etching the copper foil of the 0.4 mm thick and 0.8 mm thick copper clad laminates. Df). The perturbation method cavity resonator uses Agilent8722ES, a product of Agilent Co., Ltd. The results are shown in Table 2.

>>Glass transition temperature>> As for the glass transition temperature (Tg), the copper foil on both sides of the 0.8mm thick copper-clad laminate was removed by etching, and then a dynamic viscoelastic analysis device was used according to JIS C6481 and DMA (Dynamic Mechanical Analysis) was used. ) method. In the following Table 2, E'' represents the loss elastic modulus, and tanδ represents the loss tangent. The dynamic viscoelastic analysis device is manufactured by TA Instrument. The results are shown in Table 2.

>>Flame retardancy>> The copper foil on both sides of the metal foil-clad laminate obtained in each of the Examples and Comparative Examples was removed by etching. Then, a flame retardancy test was performed based on the UL94 vertical burning test method using the sample with the copper foil on both sides removed. The results are shown in Table 2.

>>Thermal Expansion>> Using a sample obtained by removing the copper foil of a copper-clad laminate with a thickness of 0.8 mm by etching, the glass cloth was measured for the insulating layer of the laminate using the TMA method (Thermo-mechanical analysis) specified in JIS C 6481. Thermal expansion coefficient (x direction, y direction and z direction), find its value. Specifically, the copper foil on both sides of the copper-clad laminate obtained above was removed by etching, and an evaluation substrate of 4.5 mm × 16 mm was produced. A thermomechanical analysis device (manufactured by TA Instrument) was used to analyze the temperature from 40 to 40°C at 10° C. per minute. The temperature was raised to 340°C, and the thermal expansion coefficients (ppm/K) in the x-direction, y-direction and z-direction from 60°C to 120°C were measured. The results are shown in Table 2.

>>Heating reduction>> Using a thermogravimetric measuring device, thermogravimetric analysis was performed on a sample obtained by removing the copper foil of the obtained copper-clad laminate with a thickness of 0.8 mm by etching under conditions of a nitrogen atmosphere and a temperature rise rate of 10° C./min. The thermogravimetric measuring device was "TGA5200" manufactured by SII NanoTechnology Co., Ltd. The results are shown in Table 2.

>>Thermal conductivity>> The density and specific heat of the copper foil laminated board obtained in each example and comparative example were measured. The specific heat was measured using a Q100 type DSC manufactured by TA Instrument. Furthermore, the thermal diffusivity of the copper-clad laminate in the thickness direction of the copper-clad laminate was measured. The thermal diffusivity was measured using a xenon flash analyzer (Bruker: LFA447Nanoflash). Thermal conductivity is calculated from the following formula. Thermal conductivity (W/m･K) = density (kg/m ³ ) × specific heat (kJ/kg･K) × thermal diffusivity (m ² /S) × 1000. The results are shown in Table 2.

>Example 4> The BMI-Bisanilin-M in Example 3 was changed to an equal amount of BMI-Bisanilin-P obtained in Synthesis Example 3, and the other procedures were carried out in the same manner. The results are shown in Table 2 below.

>Comparative Example 4> The BMI-Bisanilin-M in Example 3 was not used, and the content of MIR-3000 was changed to 50 parts by mass. The other procedures were carried out in the same manner. The results are shown in Table 2 below.

[Table 2]

It can be seen from the above results that the copper foil laminated boards of Examples 3 and 4 can maintain the same good varnish appearance, good prepreg appearance, high peel strength, high bending physical properties, low water absorption, and low thermal expansion coefficient as Comparative Example 4. , and thermal conductivity, and compared with Comparative Example 4, higher Tg and smaller heating loss can be achieved. In addition, the electrical characteristics (lower Dk and lower Df) are also improved.

without

Claims (16)

A resin composition containing: a cyanate ester compound (A), and a bismaleimide compound (B) represented by the following formula (1); the cyanate ester compound (A) is selected from naphthol aromatic compounds. At least one of the group consisting of an alkyl type cyanate ester compound, a naphthyl ether type cyanate ester compound, a ginsenophenolmethane type cyanate ester compound, and an adamantane skeleton type cyanate ester compound;

In ^the formula ( ¹ ) ^, Each independently represents an integer from 0 to 2. For example, the resin composition of claim 1, wherein the bismaleimide compound (B) is represented by the following formula (2);

For example, the resin composition in Item 1 or 2 of the patent application further contains a solvent. For example, the resin composition of Item 1 or 2 of the patent application, wherein the bismaleimine compound (B) contains The amount accounts for 0.1~30% by mass in the resin composition. For example, the resin composition of Item 1 or 2 of the patent scope, wherein the content ratio of the cyanate ester compound (A) and the bismaleimine compound (B) is based on the bismaleimine compound ( The equivalent ratio of the unsaturated acyl imine group of B) to the cyanate ester group of the cyanate ester compound (A) (equivalent of unsaturated acyl imine group/equivalent of cyanate ester group) is 0.01 or more and not Up to 1.1. For example, the resin composition of Item 1 or 2 of the patent application further contains maleimide compounds, epoxy resins, phenolic resins, and oxygen heterocycles other than the bismaleimine compound (B). Butane resin, benzo

Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds More than one type in the group. For example, the resin composition of Item 1 or 2 of the patent application further contains filler (C). For example, in the resin composition of Item 7 of the patent application, the content of the filler (C) is 50 to 1600 parts by mass relative to 100 parts by mass of the total resin components in the resin composition. For example, the resin composition in Item 1 or 2 of the patent application scope is a low dielectric constant material and/or a low dielectric loss tangent material. A hardened product is a hardened product of the resin composition according to any one of items 1 to 9 of the patent application. A prepreg is formed from a base material and a resin composition according to any one of items 1 to 9 of the patent application. A metal foil-clad laminate includes a layer made of at least one prepreg as claimed in claim 11, and a metal foil disposed on one or both sides of the prepreg layer. A resin sheet includes: a support, and a layer formed of a resin composition as described in any one of items 1 to 9 of the patent application, arranged on the surface of the support. A printed wiring board includes an insulating layer and a conductor layer disposed on the surface of the insulating layer; the insulating layer includes a layer made of a resin composition as described in any one of items 1 to 9 of the patent application. A method for manufacturing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1); including adding the cyanate ester compound (A), the step of mixing the bismaleimide compound (B) and a solvent, and the content of the bismaleimide compound (B) accounts for 0.1 to 30 mass% in the resin composition; the cyanic acid The ester compound (A) is selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthyl ether type cyanate ester compounds, ginsenophenol methane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. At least one of the groups;

In ^the formula ( ¹ ) ^, Each independently represents an integer from 0 to 2. For example, the manufacturing method of the resin composition in Item 15 of the patent application further contains maleimide compounds, epoxy resins, phenolic resins, oxane compounds other than the bismaleimine compound (B). cyclobutane resin, benzo

Compounds, compounds with polymerizable unsaturated groups, modified polyphenylene ethers terminally modified with substituents containing carbon-carbon unsaturated double bonds (except maleimide), elastomers and active ester compounds More than one type in the group.